CN1291965C - Method for preparing hexane diacid by nitric acid catalyzed oxidation of cyclohexane oxidized liquid acid washing water - Google Patents
Method for preparing hexane diacid by nitric acid catalyzed oxidation of cyclohexane oxidized liquid acid washing water Download PDFInfo
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- CN1291965C CN1291965C CN 200510016208 CN200510016208A CN1291965C CN 1291965 C CN1291965 C CN 1291965C CN 200510016208 CN200510016208 CN 200510016208 CN 200510016208 A CN200510016208 A CN 200510016208A CN 1291965 C CN1291965 C CN 1291965C
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Abstract
The present invention discloses a method for preparing hexane diacid by the nitric acid catalyzed oxidation of cyclohexane oxidized liquid acid washing water, which belongs to a technique for preparing hexane diacid. The method comprises the following steps: washing a cyclohexane oxidized liquid at a normal temperature and pressure according to the mass ratio of 0.1 to 2.0 of water to a cyclohexane oxidized liquid; concentrating the washed acid water; oxidizing the washed acid water by nitric acid under the action catalysts comprising vanadium; crystallizing, filtering and drying the oxidized solution to obtain crude hexane diacid; recrystallizing to obtain refined hexane diacid whose purity is above 99 %. The present invention has the advantages of simple reaction processes, low production cost, high recovery ratio of hexane diacid products and high purity of obtained hexane diacid, and the obtained hexane diacid can be directly used as fiber-grade raw materials.
Description
Technical field
The present invention relates to a kind of method, belong to preparation hexanodioic acid technology with the cyclohexane oxidation liquid pickling water preparing hexane diacid by nitric acid catalyzed oxidation.
Background technology
The direct oxidation of hexanaphthene air prepares in the process of pimelinketone and hexalin, except principal product, ε-the hydroxycarboxylic acid that also has about 10% diprotic acid, monoprotic acid and partial oxidation, by products such as lactone and superoxide (caproic acid hydrogen peroxide) and a spot of polymkeric substance.The existence of these by products has seriously influenced normally carrying out of post-order process, must separate it from principal product by processes such as washings.
The existing a large amount of patent of preparation hexanodioic acid and binary nitration mixture from the acid washing water of air oxidation of cyclohexane liquid, these patents probably can be divided into two big classes, and a class is to reclaim by physical method; Another kind of is to produce hexanodioic acid by the method for chemical reaction.
Patent GB806660, GB1015828 and GB950543 make raw material with the washing sour water of air oxidation of cyclohexane liquid, use chloroform, 1, extraction agents such as 2-ethylene dichloride are got rid of the impurity of overslaugh crystallization of adipic acid, crystallization of adipic acid is come out, the content of hexanodioic acid is 60% in the gained hexanodioic acid filter cake by this method, and the rate of recovery of hexanodioic acid is 65%.
Patent US3,023,238 by adding Nitromethane 99Min. and nitro hexane in washing water, makes their water in acid washing water form azeotrope and steam together, and obtains crystallization of adipic acid at last, and the content of the hexanodioic acid that makes by this method is 83%.
Patent US4,076,948, US4,082,788 and US4,316,775 have introduced by diprotic acid and alcohol reaction and have generated ester, and the method through rectifying prepares diprotic acid by making ester again.
Patent JP-B-SH053-33567, US3,524,892, US3,985,814, DE-A-1,957-396 etc. relate to hexanodioic acid in the water lotion and 6 hydroxycaproic acid are converted into 1 by hydrogenation reaction, 6-hexylene glycol and recycling.
The patent US6 of the petrochemical industry Development Co., Ltd application of tw Taiwan, 063,958, introduced from the alkaline wash of cyclohexane oxide solution, by steps such as extraction, rectifying, reclaim hexanodioic acid and 6 hydroxycaproic acid in the alkaline wash, the total yield of two kinds of materials is 54.7%.
Patent US6,015,924 has introduced the hexanodioic acid of two-step approach recycled fiber level, the first step at first becomes hydroxycaproic acid to the hydrogen peroxide caproic acid in the acid washing water by hydrogenation reaction, second step was used nitric acid oxidation reaction liquid, and crystallization gets hexanodioic acid then, and recrystallization gets the hexanodioic acid elaboration of fibre-grade.
The patent CN119 of the Liaoyang petro-chemical fiber company application of China, 3009A produces washing sour water in pimelinketone and the hexalin process with air oxidation of cyclohexane, heating evaporation concentrates under normal pressure or decompression, concentrated solution is under normal pressure then, temperature is to carry out pyrolysis between 90-105 ℃, generally need 4-6h, or carry out cartalytic decomposition effect as catalyzer with variable valency metal ions, generally need 1.0-3.0h, mixed solution after the decomposition under 35-78 ℃ of condition with nitric acid with 1.0: oxidizing reaction is carried out in the preparation of the weight ratio of 0.8-1.2, generate the mixed solution of hexanodioic acid and diprotic acid oxidizing reaction, mixed solution is through enrichment, crystallization, filter, dry and activated carbon treatment gets smart hexanodioic acid, crystalline mother solution is through enrichment, crystallization gets diprotic acid, patent only illustrated and made adipic acid product to get concentration be 99.75%, but do not illustrate that product gets yield, and the amount of gained binary nitration mixture is approximately half of hexanodioic acid.
Although there are various methods to prepare hexanodioic acid and binary nitration mixture, they all have such-and-such following shortcoming:
(1) reaction process complexity, the production cost height.
(2) the hexanodioic acid purity that makes is not high, can not directly be used as the raw material of fibre-grade.
(3) rate of recovery of adipic acid product is not high.
Summary of the invention
Purpose of the present invention just provides a kind of method with the cyclohexane oxidation liquid pickling water preparing hexane diacid by nitric acid catalyzed oxidation, and this procedure is simple, the yield height of hexanodioic acid.
The present invention is realized that by following technical proposals a kind of method with the cyclohexane oxidation liquid pickling water preparing hexane diacid by nitric acid catalyzed oxidation is characterized in that comprising following process:
1. under normal pressure, by water and cyclohexane oxide solution mass ratio is 0.1-2.0, water washs cyclohexane oxide solution, obtains containing the acid washing water that comprises hexanodioic acid, alcohol acid, lactone, superoxide and monocarboxylic acid mixture, and wherein organic mass content is 15-25%.
2. the acid washing water of step 1 is concentrated under normal pressure or decompression and obtain the gelled acid wash water, organic mass content is 45-55% in the gelled acid wash water, wherein the mass content of hexanodioic acid is 70-85% in the organism, the mass content of alcohol acid is 5-10%, the mass content of superoxide is 2-3%, and all the other are monocarboxylic acid and lactone.
3. to the gelled acid wash water of step 2,40-60 ℃ add vanadium down and add a kind of in copper, cobalt, titanium, nickel, the cadmium or two kinds carry out catalytic oxidation for catalyzer and nitric acid, catalyst consumption is the 0.1-0.01% of the quality of gelled acid wash water; The mass concentration of used nitric acid is 40-65%, and every 100g gelled acid wash water nitric acid dosage is 30-70ml; Oxidizing reaction is carried out 0.5-3.0h.
4. the oxidation liquid to step 3 makes the thick hexanodioic acid that mass content is 90-95% at 20-25 ℃ through crystallization, filtration.
5. to the thick hexanodioic acid of step 4, carry out making behind the recrystallization mass content and be the smart hexanodioic acid more than 99.0%.
Above-mentioned vanadium catalyst is Vanadium Pentoxide in FLAKES, ammonium vanadate or sodium metavanadate; Metal ion mass ratioes a kind of or two kinds of mixtures are 1 in vanadium and copper, cobalt, titanium, nickel, the cadmium: 2-1: 5.
The invention has the advantages that reaction process is simple, production cost is low.The rate of recovery height of adipic acid product, the hexanodioic acid purity height that makes can directly be used as the raw material of fibre-grade.
Embodiment
The invention will be further described below by embodiment:
Embodiment 1
In reactor, add the 100g organic content and be the concentrated solution of the washing sour water of 49% cyclohexane oxide solution, add 60ml 65% salpeter solution, 0.2g the salpeter solution of copper and 0.1g sodium metavanadate catalyzer, control reaction temperature is at 45-50 ℃, reaction was carried out 120 minutes, reaction solution is naturally cooled in air about 20 ℃, filtration drying gets the thick hexanodioic acid of 40.5g, thick hexanodioic acid is dissolved in again carries out recrystallization in the 100ml water, getting 34.5g purity is 99.5% smart hexanodioic acid, two subcrystalline mother liquors are merged, and evaporation concentration gets the nitration mixture of 11.2g.
Comparative Examples 1
In reactor, add the 100.2g organic content and be the concentrated solution of the washing sour water of 49% cyclohexane oxide solution, add 60ml 65% salpeter solution, 0.2g the salpeter solution of copper and 0.1g sodium metavanadate catalyzer, control reaction temperature is at 45-50 ℃, reaction was carried out 120 minutes, reaction finishes the back under 70 ℃, adding the 8g gac decolours, filtered while hot after 3 hours, filtrate is cooled to 20 ℃ and carries out crystallization, and filtration drying gets the thick hexanodioic acid of 28.6g, thick hexanodioic acid is dissolved in again carries out recrystallization in the 50ml water, getting 22.3g purity is 98.2% smart hexanodioic acid, and the rate of recovery of present embodiment hexanodioic acid is the rate of recovery 65.6% of embodiment 1 hexanodioic acid.
Embodiment 2
Add the 100g organic content and be the concentrated solution of the washing sour water of 49% cyclohexane oxide solution in reactor, control reaction temperature is at 75-80 ℃, and all the other are with embodiment 1, at last 28.3g purity be 99.6% smart hexanodioic acid.
Embodiment 3
At first will wash the processing of decolouring of the resin post of sour water by φ a 50 * 400mm, get the washing sour water of 310g, under 0.0082-0.05Mpa pressure, concentrate, the 105g organic content is 52% concentrated solution, put into oxidation reactor, add the nitric acid that 60ml has dissolved 0.12g Vanadium Pentoxide in FLAKES and 0.2g copper, at 45-50 ℃ of reaction 120min, all the other get the smart hexanodioic acid of 26.5g, the nitration mixture of 17.6g with example 1.
Embodiment 4
Adding 50% the salpeter solution of 80ml at oxidation reactor, add 0.15g Vanadium Pentoxide in FLAKES and 0.26g copper oxide catalyst then, about 50 ℃, catalysis is all dissolved, drip the 101.2g organic content then and be the concentrated solution of the washing sour water of 49% cyclohexane oxide solution, 80min is carried out in reaction, all the other are with example 1, and getting 34.2g purity at last is 99.27% smart hexanodioic acid.
Embodiment 5
Adding 65% the salpeter solution of 120ml at oxidation reactor, add 0.12 vanadium pentoxide catalyst and 0.24g copper oxide catalyst then, about 50 ℃, catalysis is all dissolved, drip the 300.2g organic content then and be the concentrated solution of the washing sour water of 49% cyclohexane oxide solution, 180min is carried out in reaction, all the other are with example 1, and getting 118g purity at last is 99.5% smart hexanodioic acid, the binary nitration mixture of 18.2g.
Claims (2)
1. method with the cyclohexane oxidation liquid pickling water preparing hexane diacid by nitric acid catalyzed oxidation is characterized in that comprising following process:
1) under normal pressure, by water and cyclohexane oxide solution mass ratio is 0.1-2.0, water washs cyclohexane oxide solution, obtains containing the acid washing water that comprises hexanodioic acid, alcohol acid, lactone, superoxide and monocarboxylic acid mixture, and wherein organic mass content is 15-25%;
2) acid washing water of step 1) is concentrated under normal pressure or decompression obtain the gelled acid wash water, organic mass content is 45-55% in the gelled acid wash water, wherein the mass content of hexanodioic acid is 70-85% in the organism, the mass content of alcohol acid is 5-10%, the mass content of superoxide is 2-3%, and all the other are monocarboxylic acid and lactone;
3) to step 2) the gelled acid wash water, 40-60 ℃ add down vanadium and add a kind of in copper, cobalt, titanium, nickel, the cadmium or two kinds carry out catalytic oxidation for catalyzer and nitric acid, catalyst consumption is the 0.1-0.01% of the quality of gelled acid wash water; The mass concentration of used nitric acid is 40-65%, and every 100g gelled acid wash water nitric acid dosage is 30-70mL; Oxidizing reaction is carried out 0.5-3.0h;
4) oxidation liquid of step 3) makes the thick hexanodioic acid that mass content is 90-95% at 20-25 ℃ through crystallization, filtration;
5), carry out making behind the recrystallization mass content and be the smart hexanodioic acid more than 99.0% to the thick hexanodioic acid of step 4).
2. by the described method for preparing hexanodioic acid of claim 1, it is characterized in that vanadium catalyst is Vanadium Pentoxide in FLAKES, ammonium vanadate or sodium metavanadate; Metal ion mass ratioes a kind of or two kinds of mixtures are 1 in vanadium and copper, cobalt, titanium, nickel, the cadmium: 2-1: 5.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101016245B (en) * | 2007-02-17 | 2010-08-04 | 青岛伊科思技术工程有限公司 | Preparing method for mixed dibasic acid ester from adipic acid production waste liquid and treatment method for the waste liquid |
| CN102190575B (en) * | 2010-03-15 | 2013-10-16 | 中国石油化学工业开发股份有限公司 | Method for recovering binary acid from waste alkali liquor in cyclohexane oxidation |
| CN102757332B (en) * | 2011-04-27 | 2015-07-01 | 中国石油化工集团公司 | Processing method of cyclohexane oxidation products |
| CN103257111A (en) * | 2012-02-16 | 2013-08-21 | 中国石油天然气股份有限公司 | Analysis method of nitrate content in purified adipic acid |
| CN103787540B (en) * | 2014-01-16 | 2015-02-18 | 新疆蓝德精细石油化工股份有限公司 | BI waste liquor recycling method |
| CN104030912B (en) * | 2014-05-23 | 2015-12-02 | 重庆华峰化工有限公司 | A kind of eco-friendly recovery Utilize Cyclohexane Oxidation By-Product prepares the technique of diprotic acid |
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